Gosavi, Shachi and Marcus, R. A. (2000) Nonadiabatic Electron Transfer at Metal Surfaces. Journal of Physical Chemistry B, 104 (9). pp. 2067-2072. ISSN 1520-6106. doi:10.1021/jp9933673. https://resolver.caltech.edu/CaltechAUTHORS:20150316-132413291
Full text is not posted in this repository. Consult Related URLs below.
Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20150316-132413291
Abstract
The present article treats the role of the density of electronic states ρ_F at the Fermi level of a metal in affecting the rate of nonadiabatic electron transfer. The rate constant k_(ET) is calculated for the electron transfer across an alkanethiol monolayer on platinum and on gold. The ρ_F of platinum is about 7.5 times that of gold, the difference being mainly due to the d band of Pt. In spite of this difference, the electron transfer rate constant k_(ET) calculated in the present paper increases only by a factor of about 1.8, instead of the factor of about 7.5 expected using ρ_F alone. Implications of these results for present and past experiments are described. Bands which are weakly coupled (e.g., the d-band of Pt in the present case) contribute much less to the rate constant than is suggested by their density of states ρ_F. Thereby, k_(ET) is approximately independent of ρ_F in two cases: (1) adiabatic electron transfer and (2) nonadiabatic electron transfer when the extra ρ_F is due to the d electrons. Experiments which can test the latter are discussed.
| Item Type: | Article | |||||||||
|---|---|---|---|---|---|---|---|---|---|---|
| Related URLs: |
| |||||||||
| ORCID: |
| |||||||||
| Additional Information: | © 2000 American Chemical Society. Received: September 21, 1999. Published on Web 02/12/2000. We thank Professors Finklea and Forster for insightful discussions and kindly sharing their data with us. It is a pleasure to acknowledge the support of this research by the National Science Foundation and the Office of Naval Research. | |||||||||
| Funders: |
| |||||||||
| Issue or Number: | 9 | |||||||||
| DOI: | 10.1021/jp9933673 | |||||||||
| Record Number: | CaltechAUTHORS:20150316-132413291 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20150316-132413291 | |||||||||
| Official Citation: | Nonadiabatic Electron Transfer at Metal Surfaces Shachi Gosavi and and R. A. Marcus The Journal of Physical Chemistry B 2000 104 (9), 2067-2072 DOI: 10.1021/jp9933673 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 55797 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | Tony Diaz | |||||||||
| Deposited On: | 16 Mar 2015 21:12 | |||||||||
| Last Modified: | 10 Nov 2021 20:50 |
Repository Staff Only: item control page
